Process and apparatus for producing hydrogen peroxide



Aug: 25, 1936. F. KRAuss ET AL PROCESS AND APPARATUS FOR PRODUCING HYDROGEN PEROXIDE Filed May 31, 1934 wx Ma VA v /n ventor:

Patented Aug; 25, 1935 umre sures PATENT OFFICE lNG HYDROGEN PEBOED d Krauss,

Brunswick, and

Ferdinan Adolf Kiipke, mm. Germany Limitation May 31, 1934, No. 328,292

' II Germany March 3, 1929 2 Claims. (Cl. 204-9) This invention relates to a process and apparatus for the production of hydrogen peroxide, more especially to. the continuous production of hydrogen peroxide by a combination of electrol- 5 ysis and distillation, the electroylte being prepared once for all so that no additions are required during all the following operations.

In carrying out the invention, an aqueous solution of sulphuric acid and ammonium bisull phate is subjected to electrolysis resulting in the production of a solution containing ammonium persulphate besides free acid and the latter solution is subjected to distillation, preferably under vacuum. During the distillation the am- 15 monium persulphate reacts with the water to produce hydrogen peroxide which is separated out of the solution by distillation.

According to the invention the electrolysisis carried out in an electrolyzer in which the elec- 20 trodes are not separated by a porous diaphragm and the electrolyte consisting of an acid solution of ammonium bisulphate is kept flowing. .The electrolysis however is not carried to the point where all of the ammonium bisulphate is wholly g converted to ammonium persulphate or salts are precipitated. The solution subjected to electrolysis is acidified with sulphuric acid as to produce a specific gravity of at least 1.2. The

. process is a continuous one and requires no fur- 30 titlinadditionoi' sulphuric acid during its opera on.

In carrying out .the continuous process the acid persulphate solution obtained by electrolysis is fed continuously and streams through the dis- 5 tilling apparatus without, as already mentioned, anylfurther addition of sulphuric acid. The electroiyzer and the distilling apparatus may be separated from each other, or they may be combined in which case the whole of the process 40 may be carried out automatically. In the distilling apparatus, the persulphate is reconverted into bisulphate by heat u'nder partial consumption of the water contained in the solution, hydrogen peroxide being simultaneously formed so that the resulting solution will have the same bisulphate and sulphuric acid content as the solution before electrolysis. The solution is with drawn from the distilling'apparatus in a con- 50 tinuous flow and, after the addition thereto of the lost water, fed again into the electrolytic cell. The hydrogen peroxide is continuously distilled oil and the condensate is also withdrawn from the apparatus in a continuous stream.

55 The difflculty with accomplishing such distilla-- tion is that it is necessary to work with thin layers in order to obtain a satisfactory yield. In hitherto known distilling apparatus, the solution used flows in a thin sheet on the inner walls of externally heated pipes. This has the 5 disadvantage that the escaping vapors come into contact with the downwardly flowing solution. According to the present invention the distillation is carried out preferably under vacuum with thin layers and with profitable yield, the disadvantages of the old processes being eliminated. The pipes of the present apparatus are heated from the inside, and the solution flows along the outside of the pipes. In this manner the driven off vapors can easily be withdrawn from the dis- 15.

tillation zone and prevented from coming into furthercontact with the flowing solution. The outer surfaces of the outer jackets of the apparatus may be heated in order to maintain a uniform temperature in the interior of the apparatus.

As a modification the outer walls may be cooled, the effect of which will be that the solution to be distilled only comes into contact at one side with a heated surface and that the' 5 vapors escaping from the other side enter a space having a much lower temperature so that they are immediately removed under rapid condensation.

. A suitable apparatus for carrying out the invention may be constructed in such a manner that the solution is made to flow in thin layers along the outer surface of vertical or inclined, internally heated pipes or the like. The heating can be effected in any suitable mannerfii'or instance, by means of steam, electric current or the like. The pipes may be encircled by an outer jacket which is cooled and from whichthe rapidly condensing vapors given ofl' by the thin layer of the solution, can be readily removed from the 40 distillation zone. I g

The accompanying drawing wherein like characters denote corresponding parts in the several views, shows the essential parts of a plant for carrying out the invention. Other parts such as circulation and vacuum pumps, connecting pipes, heating elements, cooling devices, sources of electric current, etc. are not illustrated as being common in the art. i

Figure 1 is a vertical section through'that part o! the apparatus in which electrolysis is effected.

Figure 2 is a view partly in elevation and partly in section disclosing a modified form of the ap- Figure 3 is a view similar to Figure 2 showing a further modification of the electrolytic'apparatus.

Figure 4 is a vertical section disclosing one form.

or the apparatus in which the product of elec- 5 trolysis is subjected to distillation.

Figure5isaviewsimilar toFigureishowing a modification of the distillation apparatus, In the apparatus for carrying out the present invention, there is provided an electrolytic cell A 10 and a distilling apparatus B.

In the construction of the electrolytic cell A in Figure 1, there is provided an inner cylindrical casing b having an inverted conical bottom b Spaced uniformly from this inner casing is an 15 outer casing consisting oi a cylindrical body a having a conical bottom a from the apex of which extends a drain pipe I. These casings are suitably supported by an insulation (not shown) so that each is insulated from the other and from 20 all extraneous parts of the apparatus and are connected by conductors a and b to a suitable source of electric current so that they may form the electrodes of the electrolytic cell. A pump is 7 connected to the space e between the anode and 25 cathode by pipe I and, as will be presently understood, a continuous flow of electrolytic solution is maintained by the pump through this space. Within the inner casing b is a jacket or jacket casing b which is spaced from the inner. casing 30' or electrode and through the space formed thereby a cooling medium.may be circulated. Similarly there is a jacket c spaced'outside the outer electrode and a cooling hold may also be circulated through the space (2 thus provided.

85 Toincrease the cathodic or anodic density of current the electrodes may be formed, as shown in Figures 2 and 3, of a non-conducting body or hollow body provided with numerous holes which are suitably filled with a conductor such as lead.

40 The non-conducting bodymay consist of an inert material such as quartz, glass, porcelain or the like. The holes may have the form of circles, squaresorothershapesthedistanceotwhich from one another and from the cathode or anode 45 respectively is made nearly equal.

As already mentioned the electrolysis is eiiected without precipitating any salt and only up to a point where the current output begins to unduly decrease. A satisfactory working of the electrolysis is easily obtained by r gulating thfirateofflowoftheelectrolytepassingthe ce Theoutput canbeincreasedbyreducing the free space between the electrodes. For instance, 55 it has been proved advantageous to introduce suitably shaped bodies oiinert material such as glass into the flowing electrolyte.

It maybenotedthattheapparatusandtherewith the anode may have another form than that ,mofaiunnelaridthatifde'siredonlyapartcjf k and tube. By this means, liquid flowing downwardly from the tunnel 1: forms a thin sheet surroimding the hot tube so that distillation of 75 the volatile constituents of such liquid is readily obtained. The pipe in leads'irom the electrolytic cell to the upper part of the tunnel k At the lower end of the casing there is provided a funnel which surrounds the tube It so that the residue from the distillation flowing down said tube will readily find it's way into the tunnel.

A pipe '0 leads from the lower part of the funnel o to a circulating pump on its suction side. It will now be readily understood that a continuous circulation of fluid is maintained through the electrolytic and distilling sections of the apparatus.

The vapors may be withdrawn by pipes 112. pro-- vided at spaced points in the wall i and connected with a vacuum pump, or the casing 1'. may be suitably cooled and the condensate withdrawn by pipe 11..

It is preferable to introduce into the utilizable part of the evacuated space filling bodies as, tor instance, the so called Raschig rings, to multiply a the active surface of the distilling apparatus.

. lnl igure5pisaninclineddistilling facealong which the liquid to be distilled which is introduced at qruns down in a'thin layer. This distiJling face-is, for instance, heated by steam flowing through the space 1' in the direction of the arrows. The vapors developed out of the thin layer flowing down enter the chambers s from whichthey are wholly or partly removed by pipes t, the condensing part, if any, down the uiding faces 1:. and the cooled wall v and being likewise at once removed by the collectingpipe w from the distillation zone.

."I'heplantmaybeoperatedwithmitpeculiar dimculties automatically. For this purpon, for instance, the bisulphate solution leaving the evacuated 11800319 5 8 and distillation apparatusas well as the hydrogen peroxide flowing oil may be separately conducted by means of twoor three-way-cocks or the like intcone or more 001- lecting receivers, Other containers likewise connected with thesaid cocks are discharged under atmospheric, pressure, the cocks being automatically reversed assoon as the containers are full so that the full containers are discharged under atmospheric pressure, whereas the containers previously discharged are filled again.

The following is an enrnple or the process:

For the production of hydrogen peroxide. a quantity of 920 g. sulphuricacid was added to I; solution 015-290 g. ammonium hisulphate in 500 oil water. After subjection to electrolysis, the liquid contained about 230 g. ammtmum per-' sulphate and about 58 g. ammonium bisulphate. Thiswas ted in a thin layer into the apparatus according to the invention and heated therein; and the hydrogen peroxide formed by the action :ituthe sulphuric acidonthepersulphatewasdis ed oil.

Theoretically itshould be possible to-obtainlio from a solution of 230 g. ammonium persulphate about 140.3'g. oi a 30% hydrogen peroxide 11- tion, Actually-109.86 g. were obtained in the above described distillation plant so that the yield oi hydrogen peroxide was over 96%. 05

No separation of salts took place during the 'processandnoadditidnotsulphuricaeidduring the process was required. Y

. The polution'discharged from the distillingapparatus had the original sulphuric acid content; iii

namely, 920g.andalsotheoriginal contentot. ammoniuin bisulphate, namely, 290 g.

The above described will, as compared with known apparatus, bring about the following advantages: it

I. The distance between the cathode and the anode is uniform, and nearly the same current density is obtained at all points.

2. The entire electrolyte will be transversed by the current, and no dead spaces through which little. or no current flows, will occur, as do in a commonelectrolytic bath.

3. Owing to the absence of dead spaces there will be no decomposition of formed products, whereby the output will be increased.

4. Since the electrodes themselves form the walls of the cell, and no special containers of glass or the like, since on the one hand the surface area is greater and since the heat conductivity of the metal is greate 6. A further important advantage is the feature that no separation of salts takes place either during the electrolysis or during the distillation for which reason the electrolysis as well as the distillation can proceed without interruption.

All these'advantag'es lead to a much greater current output than that obtained by the usual processes.

The apparatus shown in Figure 4, moreover, al lows the use of a heating medium which is under pressure in spite of the comparatively thin wall of the inner pipe. This advantage is particularly pronounced when the distillation space is under vacuum, since the thickness of the wall can be much thinner when the pressure is inside and the vacuum outside the pipe instead of vice versa.

The thin wall promotes the heat exchange and thus saves the distillation heat.

We claim:-

1. The method of producing ammonium persulphate by electrolyzing ammonium bisulphate which comprises passing a solution of ammonium bisulphate and sulphuric acid having a specific gravity of at least 1.2 as an electrolyte between an anode presenting a continuous active surface and a cathode having a surface of substantially the same extent but consisting of relatively small conducting areas spaced throughout its surface' and separated by non-conducting areas, said,

electrolyte passing in direct contact with both the anode and the cathode.

2;- An electrolytic cell suitable for use in producingammonium persulphate by electrolysis of ammonium bisulphate having cylindrical elec-' trodes which nest relatively closely one within the other to provide an inter-electrode electrolytecontaining space through which the electrode flows and of which the active surfaces are uniformly spaced apart, the anode serving as the wall of the cell and the cathode having its active surface restricted over the entire area thereof and consisting of relatively small conducting areas and non-conducting areas separating said conducting areas.

FERDINAND KRAUSS. snow KOPKE. 

